Imaging device, manufacturing device, and manufacturing method

ABSTRACT

The present technology relates to an imaging device, a manufacturing device, and a manufacturing method. The imaging device includes an organic photoelectric conversion film, an upper electrode provided in an upper portion of the organic photoelectric conversion film, a lower electrode provided in a lower portion of the organic photoelectric conversion film, and a metal thin film provided between the organic photoelectric conversion film and the upper electrode or between the organic photoelectric conversion film and the lower electrode. The metal thin film is provided between the organic photoelectric conversion film and the upper electrode. The upper electrode is formed of an oxide semiconductor, a metal oxide, and the metal thin film. The present technology can be applied to a vertical spectral imaging device.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/126,756 filed on Sep. 10, 2018, which is a continuation of U.S.patent application Ser. No. 15/512,550, filed Mar. 18, 2017, now U.S.Pat. No. 10,074,696, which is a National Stage Entry of PatentApplication No. PCT/JP2015/077011 filed Sep. 25, 2015, which claimspriority benefit of Japanese Patent Application No. JP 2014-205442 filedin the Japan Patent Office Oct. 6, 2014. Each of the above-referencedapplications is hereby incorporated herein by reference in its entirely.

TECHNICAL FIELD

The present technology relates to an imaging device, a manufacturingdevice, and a manufacturing method. Specifically, the present technologyrelates to an imaging device, a manufacturing device, and amanufacturing method preferably used to reduce an influence of hydrogen.

BACKGROUND ART

In recent years, in a charge coupled device (CCD) image sensor or acomplementary metal oxide semiconductor (CMOS), a pixel size has beenreduced. Therefore, sensitivity is lowered due to reduction in thenumber of photons incident on a unit pixel, and an S/N ratio is lowered.In addition, in a presently widely-used pixel array in which pixels ofred, green, and blue are arranged on a plane, for example, in a Bayerarray using a primary color filter, for example, in a red pixel, greenand blue light does not pass through the color filter and is not usedfor photoelectric conversion, and therefore sensitivity is lost. Inaddition, when an interpolation process is performed between pixels, afalse color may be generated due to generation of a color signal.

An image sensor to obtain three color photoelectric conversion signalswith one pixel by stacking three photoelectric conversion layers in avertical direction has been proposed. In Patent Document 1, as such astructure for stacking three color photoelectric conversion layers withone pixel, for example, a sensor in which a photoelectric conversionunit for detecting green light and generating a signal chargecorresponding thereto is provided above a silicon substrate and bluelight and red light are detected by two photodiodes stacked in thesilicon substrate has been proposed.

In addition, Patent Document 2 has proposed a back surface irradiationtype structure provided with a photoelectric conversion film 1 layerabove a silicon substrate, having a two color photoelectric conversionunit in the silicon substrate, and having a circuit-forming surfaceformed on a side opposite to a light-receiving surface. When a backsurface irradiation type organic photoelectric conversion layer isformed, a circuit, wiring, or the like is not formed between aninorganic photoelectric conversion unit and an organic photoelectricconversion unit. Therefore, a distance between the inorganicphotoelectric conversion unit and the organic photoelectric conversionunit in the same pixel can be close to each other. Therefore, dependenceof colors on an F value can be suppressed, and fluctuation insensitivity between the colors can be suppressed.

CITATION LIST Patent Document

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-332551

Patent Document 2: Japanese Patent Application Laid-Open No. 2011-29337

Patent Document 3 Japanese Patent Application Laid-open No. 2008-252004

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

An organic photoelectric conversion film is generally susceptible towater or oxygen, and therefore it is necessary to form a sealingstructure in an upper layer of an organic photoelectric conversion film.For example, Patent Document 3 has proposed formation of a sealingstructure formed by stacking a SiN film formed by a sputtering methodand an AlO film formed by an ALD method.

However, when such a sealing film is formed, the ALD method needs to usean organic metal such as trimethylaluminum (TMA) as a precursor, andhydrogen in the precursor may be diffused to upper and lower transparentelectrodes. As a result of diffusion, not only the upper electrode butalso the lower electrode is reduced, a work function becomes shallow,and an organic photoelectric conversion efficiency may be deteriorated.

The lower electrode preferably has a deep work function, and the upperelectrode preferably has a shallow work function. This is because thiscan reduce a dark current by making an electron injection barrier fromthe lower electrode higher, and can improve a carrier extractionefficiency by increasing an internal electric field.

Therefore, as described above, it is desired to prevent diffusion ofhydrogen in the precursor to the lower transparent electrode, reductionof the lower electrode, shallowing of the work function, anddeterioration of an organic photoelectric conversion efficiency.

The present technology has been achieved in view of such a situation,and makes it possible to prevent conversion of the work function due todiffusion of hydrogen and deterioration in the organic photoelectricconversion efficiency.

Solutions to Problems

An imaging device in an aspect of the present technology includes anorganic photoelectric conversion film, an upper electrode provided in anupper portion of the organic photoelectric conversion film, a lowerelectrode provided in a lower portion of the organic photoelectricconversion film, and a metal thin film provided between the organicphotoelectric conversion film and the upper electrode or between theorganic photoelectric conversion film and the lower electrode.

The metal thin film is provided between the organic photoelectricconversion film and the upper electrode. The upper electrode can beformed of an oxide semiconductor, a metal oxide, and the metal thinfilm.

The metal oxide is aluminum oxide (AlO). The metal thin film can beformed of aluminum (Al).

The metal thin film can be formed of any one of aluminum (Al), indium(In), silver (Ag), gold (Au), zinc (Zn), lithium (Li), tin (Sn),antimony (Sb), magnesium (Mg), cadmium (Cd), calcium (Ca), potassium(K), rubidium (Rb), cesium (Cs), strontium (Sr), barium (Ba), cerium(Ce), yttrium (Y), hafnium (Hf), nickel (Ni), gallium (Ga), and titanium(Ti).

Each of the upper electrode and the lower electrode can be formed of anyone of ITO, tin oxide-based SnO2, zinc oxide-based materials aluminumzinc oxide, gallium zinc oxide, and indium zinc oxide, IGZO, CuI,InSbO4, ZnMgO, CuInO2, MgIn2O4, CdO, and ZnSnO3.

The organic photoelectric conversion film can be formed of any one of aquinacridone derivative, a naphthalene derivative, an anthracenederivative, a phenanthrene derivative, a tetracene derivative, a pyrenederivative, a perylene derivative, and a fluoranthene derivative.

The organic photoelectric conversion film can be formed of any one of apolymer of phenylene vinylene, fluorene, carbazole, indole, pyrene,pyrrole, picoline, thiophene, acetylene, or diacetylene, and aderivative thereof, a metal complex dye, a cyanine dye, a merocyaninedye, a phenylxanthene dye, a triphenylmethane dye, a rhodacyanine dye, axanthene dye, a macrocyclic azaannulene dye, an azulene dye,naphthoquinone, an anthraquinone dye, a condensed polycyclic aromaticcompound such as anthracene or pyrene, a chain compound obtained bycondensing an aromatic ring or heterocyclic compound, a heterocyclicring compound containing two nitrogen atoms and having a squaryliumgroup and a croconic methine group as a bonding chain, such asquinoline, benzothiazole, or benzoxazole, and a cyanine-like dye bondedby a squarylium group and a croconic methine group. The metal complexdye can be any one of a dithiol metal complex dye, a metalphthalocyanine dye, a metal porphyrin dye, and a ruthenium complex dye.

The metal thin film can have a thickness of 5 nm or less.

The metal thin film has a spherical shape or a predetermined shape, andcan be scattered at equal intervals or at random.

A hole blocking layer can be provided between the metal thin film andthe organic photoelectric conversion film.

An enthalpy control layer can be provided along with the metal thin filmor in place of the metal thin film.

The enthalpy control layer can be provided between the organicphotoelectric conversion film and the lower electrode.

The enthalpy control layer can be formed of any one of Ag2O, CoO, Co3O4,CdO, Cs2O, CuO, Cu2O, GeO(c), GeO2(c1), GeO2(c2), NiO(c), PbO(c),PbO2(c2), PbO2(c), PdO(c), Rb2O(c), Rb2O2(c), SeO2(c), SeO3(c), TeO2(C),Tl2O(c), and Tl2O3(c).

A manufacturing device in an aspect of the present technology forms anorganic photoelectric conversion film, forms an upper electrode in anupper portion of the organic photoelectric conversion film, forms alower electrode in a lower portion of the organic photoelectricconversion film, and forms a metal thin film between the organicphotoelectric conversion film and the upper electrode or between theorganic photoelectric conversion film and the lower electrode.

The metal thin film can be formed by vapor deposition.

The metal thin film can be formed between the organic photoelectricconversion film and the upper electrode. The upper electrode can beformed by stacking an oxide semiconductor, a metal oxide, and the metalthin film. The metal oxide can be formed by oxidization at the time offilm formation of the oxide semiconductor.

The metal thin film can be formed into a spherical shape or apredetermined shape so as to be scattered at equal intervals or atrandom.

A hole blocking layer can be further formed between the metal thin filmand the organic photoelectric conversion film.

An enthalpy control layer can be formed along with the metal thin filmor in place of the metal thin film.

A manufacturing method in an aspect of the present technology includessteps of forming an organic photoelectric conversion film, forming anupper electrode in an upper portion of the organic photoelectricconversion film, forming a lower electrode in a lower portion of theorganic photoelectric conversion film, and forming a metal thin filmbetween the organic photoelectric conversion film and the upperelectrode or between the organic photoelectric conversion film and thelower electrode.

An imaging device in an aspect of the present technology includes anorganic photoelectric conversion film, an upper electrode provided in anupper portion of the organic photoelectric conversion film, a lowerelectrode provided in a lower portion of the organic photoelectricconversion film, and a metal thin film provided between the organicphotoelectric conversion film and the upper electrode or between theorganic photoelectric conversion film and the lower electrode.

A manufacturing device and a manufacturing method in an aspect of thepresent technology manufacture the imaging device.

Effects of the Invention

According to an aspect of the present technology, it is possible toprevent conversion of a work function due to diffusion of hydrogen anddeterioration in an organic photoelectric conversion efficiency.

Note that effects of the present technology are not necessarily limitedto the effects described herein, and may include any of the effectsdescribed in the present disclosure.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram for explaining a configuration of an imaging device.

FIG. 2 is a diagram for explaining a configuration of an imaging device.

FIG. 3 is a diagram for explaining a configuration of an imaging deviceaccording to a first embodiment.

FIG. 4 is a diagram for explaining another configuration of the imagingdevice according to the first embodiment.

FIG. 5 is a diagram for explaining another configuration of the imagingdevice according to the first embodiment.

FIG. 6 is a diagram for explaining manufacturing of an imaging device.

FIG. 7 is a diagram for explaining manufacturing of the imaging device.

FIG. 8 is a diagram for explaining manufacturing of the imaging device.

FIG. 9 is a diagram for explaining manufacturing of the imaging device.

FIG. 10 is a diagram for explaining manufacturing of the imaging device.

FIG. 11 is a diagram for explaining manufacturing of the imaging device.

FIG. 12 is a diagram for explaining manufacturing of the imaging device.

FIG. 13 is a diagram for explaining manufacturing of the imaging device.

FIG. 14 is a diagram for explaining manufacturing of the imaging device.

FIG. 15 is a diagram for explaining manufacturing of the imaging device.

FIG. 16 is a diagram for explaining a configuration of an imaging deviceaccording to a second embodiment.

FIG. 17 is a diagram for explaining the configuration of the imagingdevice according to the second embodiment.

FIG. 18 is a diagram for explaining the configuration of the imagingdevice according to the second embodiment.

FIG. 19 is a diagram for explaining a configuration of an imaging deviceaccording to a third embodiment.

FIG. 20 is a diagram for explaining a configuration of an imaging deviceaccording to a fourth embodiment.

FIG. 21 is a diagram for explaining a material forming an enthalpycontrol layer.

FIG. 22 is a diagram for explaining a configuration of an electronicapparatus.

FIG. 23 is a diagram for explaining a usage example of an imagingdevice.

MODES FOR CARRYING OUT THE INVENTION

Hereinafter, modes for carrying out the present technology (hereinafter,referred to as embodiments) will be described. Note that the descriptionwill be made in the following order.

1. Configuration of imaging device2. Configuration of conventional imaging device3. Configuration of first imaging device4. Manufacturing of imaging device5. Configuration of second imaging device6. Configuration of third imaging device7. Configuration of fourth imaging device8. Configuration of electronic apparatus9. Usage example of imaging device

<Configuration of Imaging Device>

FIG. 1 illustrates a schematic configuration of an example of a CMOSimaging device applied to the present embodiment. As illustrated in FIG.1, an imaging device 1 of the present example includes a semiconductorsubstrate 11, a pixel unit (so-called imaging region) 3 in which aplurality of pixels 2 each including a photoelectric conversion unit istwo-dimensionally arranged with regularity on a silicon substrate, forexample, and a peripheral circuit unit. Each of the pixels 2 includes aphotoelectric conversion unit and a plurality of pixel transistors(so-called MOS transistors).

A plurality of pixel transistors can be formed, for example, by threetransistors of a transfer transistor, a reset transistor, and anamplification transistor. In addition, by adding a selection transistor,the plurality of pixel transistors can be formed by four transistors. Anequivalent circuit of a unit pixel is similar to a usual circuit, andtherefore detailed description thereof will be omitted. In addition, aso-called pixel shared structure in which a plurality of photoelectricconversion units shares pixel transistors other than the transfertransistor and shares floating diffusion can be applied as a pixel.

The peripheral circuit unit includes a vertical driving circuit 4, acolumn signal processing circuit 5, a horizontal driving circuit 6, anoutput circuit 7, a control circuit 8, and the like.

The control circuit 8 receives an input clock and data giving a commandof an operation mode or the like, and outputs data of internalinformation or the like of an imaging device. That is, the controlcircuit 8 generates a clock signal and a control signal serving asreferences for operations of the vertical driving circuit 4, the columnsignal processing circuit 5, the horizontal driving circuit 6, and thelike on the basis of a vertical synchronization signal, a horizontalsynchronization signal, and a master clock. Then, these signals areinput to the vertical driving circuit 4, the column signal processingcircuit 5, the horizontal driving circuit 6, and the like.

The vertical driving circuit 4 is formed, for example, of a shiftregister, selects pixel driving wiring, supplies a pulse for driving apixel to the selected pixel driving wiring, and drives the pixel inunits of rows. That is, the vertical driving circuit 4 sequentiallyselects and scans each of the pixels 2 in the pixel region 3 in units ofrows in a vertical direction, and supplies a pixel signal based on asignal charge generated in accordance with the amount of light received,for example, in a photodiode serving as a photoelectric conversionelement of each of the pixels 2 to the column signal processing circuit5 through a vertical signal line 9.

The column signal processing circuit 5 is disposed, for example, foreach of columns of the pixels 2, and performs signal processing such asremoval of a noise for a signal output from the pixels 2 in one row foreach of the pixel columns. That is, the column signal processing circuit5 performs signal processing such as CDS for removing a fixed patternnoise unique to the pixels 2, signal amplification, or AD conversion. Inan output stage of the column signal processing circuit 5, a horizontalselection switch (not illustrated) is connected and provided between thecolumn signal processing circuit 5 and a horizontal signal line 10.

The horizontal driving circuit 6 is formed of a shift register, forexample. The horizontal driving circuit 6 sequentially selects each ofthe column signal processing circuits 5 by sequentially outputting ahorizontal scan pulse, and causes each of the column signal processingcircuits 5 to output a pixel signal to the horizontal signal line 10.

The output circuit 7 performs signal processing for a signalsequentially supplied from each of the column signal processing circuits5 through the horizontal signal line 10, and outputs the processedsignal. For example, only buffering is performed, or black leveladjustment, column variation correction, various types of digital signalprocessing, and the like are performed. An input and output terminal 12exchanges a signal with the outside.

<Configuration of Conventional Imaging Device>

In order to clarify a difference between the imaging device to which thepresent technology is applied and a conventional imaging device, first,referring to FIG. 2, the conventional imaging device will be described.FIG. 2 is a diagram illustrating a configuration of a conventionalimaging device. The imaging device illustrated in FIG. 2 is a CMOSimaging device. FIG. 2 is a cross-sectional view of one pixel 20 in apixel unit of the CMOS imaging device.

An imaging device 21 is formed by stacking one organic photoelectricconversion unit 41 and inorganic photoelectric conversion units PD 36and the PD 37 having two pn junctions in the same pixel, that is, in onepixel in a depth direction.

More specifically, the imaging device 21 includes a semiconductorsubstrate (silicon substrate) 35 in which an inorganic photoelectricconversion unit is formed. A light-receiving surface on which light isincident is formed on a back surface side (upper side of the substrate35 in FIG. 2) of the substrate 35. A circuit including a read circuit orthe like is formed on a surface side of the substrate 35. That is, theimaging device 21 includes the light-receiving surface on the backsurface side of the substrate 35 and a circuit-forming surface formed ona substrate surface side opposite to the light-receiving surface. Thesemiconductor substrate 35 is formed of a first conductivity type, forexample, an n-type semiconductor substrate.

In the semiconductor substrate 35, an inorganic photoelectric conversionunit having two pn junctions, that is, a first photodiode PD 36 and asecond photodiode PD 37 are formed so as to be stacked in a depthdirection from the back surface side. In the semiconductor substrate 35,the first photodiode PD 36 is formed, and the second photodiode PD 37 isformed from the back surface side toward a depth direction (downwarddirection in FIG. 2).

In this example, the first photodiode PD 36 is for blue, and the secondphotodiode PD 37 is for red.

On the other hand, a first color organic photoelectric conversion unit41 in which upper and lower surfaces of an organic photoelectricconversion film 32 are sandwiched by an upper electrode 31 and a lowerelectrode 33 is stacked on an upper layer of a back surface of asubstrate in a region in which the first photodiode PD 36 and the secondphotodiode PD 37 are formed. In this example, the organic photoelectricconversion unit 36 is for green. The upper electrode 31 and the lowerelectrode 33 are formed, for example, of a transparent conductive filmsuch as an indium tin oxide (ITO) film or an indium zinc oxide film.

Here, description will be made by assuming that the upper electrode 31is formed of an oxide semiconductor (ITO) 51 and an aluminum oxide (AlO)thin film 52. In addition, description will be made by assuming that thelower electrode 33 is formed of an oxide semiconductor (ITO).

Here, as a combination of colors, the organic photoelectric conversionunit 41 is green, the first photodiode PD 36 is blue, and the secondphotodiode PD 37 is red. However, another color combination can be used.For example, the organic photoelectric conversion unit 41 can be red orblue, and the first photodiode PD 36 and the second photodiode PD 37 canbe set to other corresponding colors. In this case, positions of thefirst and second photodiodes PD 36 and PD 37 in the depth direction areset according to the color.

As an organic photoelectric conversion film for performing photoelectricconversion with green wavelength light, for example, an organicphotoelectric conversion material containing a rhodamine dye, ameracyanine dye, or quinacridone can be used. As an organicphotoelectric conversion film for performing photoelectric conversionwith red wavelength light, an organic photoelectric conversion materialcontaining a phthalocyanine dye can be used. As an organic photoelectricconversion film for performing photoelectric conversion with bluewavelength light, an organic photoelectric conversion materialcontaining a coumarin dye, tris-8-hydryxyquinoline Al (Alq3), ameracyanine dye, or the like can be used.

In the organic photoelectric conversion unit 41, the transparent lowerelectrode 33 is formed, and an insulating film 34 for insulating andseparating the lower electrode 33 is formed. Then, the organicphotoelectric conversion film 32 is formed on the lower electrode 33,and the transparent upper electrode 31 is formed thereon.

In the semiconductor substrate 35 in one pixel 20, a pair of wiring 39and wiring 40 is formed. The lower electrode 33 in the organicphotoelectric conversion unit 41 is connected to the wiring 39, and theupper electrode 31 is connected to the wiring 40.

For example, in order to suppress short-circuiting with Si, the wiring39 and the wiring 40 can be formed of SiO2, a tungsten (W) plug having aSiN insulating layer in the periphery thereof, or a semiconductor layerby ion implantation. In this example, a signal charge is an electron.Therefore, the wiring 39 is an n-type semiconductor layer when beingformed of a semiconductor layer by ion implantation. An upper electrodeextracts a hole, and therefore can use a p-type.

In this example, an n-type region 38 for charge accumulation is formedon a surface side of the substrate 35. This n-type region 38 functionsas a floating diffusion portion of the organic photoelectric conversionunit 41.

As the insulating film 34 on the back surface of the semiconductorsubstrate 35, a film having a negative fixed charge can be used.Examples of the film having a negative fixed charge include a hafniumoxide film. That is, the insulating film 34 may be formed of athree-layer structure obtained by sequentially forming a silicon oxidefilm, a hafnium oxide film, and a silicon oxide film from the backsurface.

On the circuit-forming surface on the surface side of the substrate 35,a plurality of pixel transistors corresponding to the organicphotoelectric conversion unit 36, the first photodiode PD 36, and thesecond photodiode PD 37 is formed. As the plurality of pixeltransistors, the above four transistor configuration or the threetransistor configuration can be used. A configuration sharing a pixeltransistor can be also used. In FIG. 2, these transistors are notillustrated.

Note that in the surface side of the semiconductor substrate 35, a pixeltransistor of a pixel unit is formed, and a peripheral circuit such as alogic circuit is formed in the peripheral circuit unit, although notillustrated. A layer containing a peripheral circuit or the like isreferred to as a multilayer wiring layer. The multilayer wiring layer isprovided on the lower side of the substrate 35 in FIG. 2, although notillustrated.

A back surface side of the semiconductor substrate 35, morespecifically, a surface of the upper electrode 31 of the organicphotoelectric conversion unit 41 is a light-receiving surface. Inaddition, an on-chip lens (not illustrated) is formed on the organicphotoelectric conversion unit 41 through a flattened film (notillustrated). In this example, no color filter is formed.

An operation (driving method) of the imaging device 21 will bedescribed. The imaging device 21 is formed as a so-called back surfaceirradiation type imaging device irradiated with light from the substrateback surface side. In this example, a fixed negative voltage VL (<0 V)is applied to the lower electrode 33 of the organic photoelectricconversion unit 36 through necessary wiring of the multilayer wiringlayer, and a voltage VU (>VL) higher than the voltage VL of the lowerelectrode 33, for example, a power supply voltage is applied to theupper electrode 31 at the time of charge accumulation. That is, thenegative voltage VL is applied to the lower electrode 33 closer to thesemiconductor substrate 35.

At the time of charge accumulation, when light is incident on one pixel20 without passing through a color filter, green wavelength light isphotoelectrically converted in the organic photoelectric conversion film32 having an absorption characteristic in the green wavelength light. Ofan electron-hole pair generated by the photoelectric conversion, anelectron serving as a signal charge is attracted by the upper electrode31 of the high potential VU.

A photoelectrically converted hole is attracted by the lower electrode33 of VL as a negative electrode. Blue wavelength light is absorbed bythe first photodiode PD 36 formed in a shallow portion close to the backsurface of the semiconductor substrate 35, is photoelectricallyconverted, and a signal charge corresponding to blue is accumulated. Thered wavelength light is absorbed by the second photodiode PD 37 formedin a deep portion from the back surface of the semiconductor substrate35, is photoelectrically converted, and a signal charge corresponding tored is accumulated.

When a charge is read, a transfer transistor (not illustrated) is turnedon. Each transfer transistor is turned on, and the accumulated signalcharges (electrons) of the organic photoelectric conversion unit 41, thefirst photodiode PD 36, and the second photodiode PD 37 are therebytransferred to floating diffusion portions (FD) corresponding thereto.Then, the red, green, and blue pixel signals are read by the verticalsignal lines through the other pixel transistors, and are output.

By the way, the above vertical spectral type imaging device needs to usea transparent electrode along with the upper electrode 31 and the lowerelectrode 33. However, a film formed at a low temperature such as an ALDmethod includes a large amount of hydrogen in the film, and reduces awork function of ITO due to hydrogen in the film when the ITO is usedfor the lower electrode 33.

The ALD method reduces a precursor with O3, and therefore a film isformed by oxidization. O3 during film formation may denaturalize ordeteriorate the organic photoelectric conversion film 32 and the lowerelectrode 33.

On the other hand, in order to transport a hole from the organicphotoelectric conversion film 32, the lower electrode 33 needs to use atransparent electrode having a high work function, and the upperelectrode 31 needs to use a transparent electrode having a low workfunction. When ITO is used for the lower electrode 33, control isperformed so as to obtain a film having a high work function by formingan O-rich film by an oxygen plasma treatment.

As described above, when the lower electrode 33 is denaturalized due toan influence of O3 during film formation, the work function may bereduced, hole transport may be inhibited, and sensitivity may belowered. That is, when the lower electrode 33 is denaturalized due to aninfluence of hydrogen or the like, and the work function is reduced,sensitivity is lowered. Therefore, it is necessary to prevent such asituation.

<Configuration of First Imaging Device>

Therefore, as a first embodiment, an imaging device suppressingreduction of a lower electrode 33 by disposing a metal thin film betweenan upper electrode 31 and an organic photoelectric conversion film 32will be described.

FIG. 3 is a diagram illustrating a configuration of an imaging devicehaving a configuration for protecting the lower electrode 33 from asubstance serving as a factor for reducing a work function of hydrogenor the like. The same reference signs are given to the same componentsas those of the imaging device 21 illustrated in FIG. 2, and descriptionthereof will be omitted appropriately.

An imaging device 101 illustrated in FIG. 3 includes a metal thin film102 in the upper electrode 31. More specifically, the metal thin film102 is provided on a lower side of an oxide semiconductor 51 and analuminum oxide (AlO) thin film 52 forming the upper electrode 31 betweenthe AlO thin film 52 and an organic photoelectric conversion unit 41.

As described above, in the first imaging device, the upper electrode 31is formed of an oxide semiconductor film, a metal oxide film, and ametal film.

As the metal thin film 102, for example, aluminum (Al) can be used.Aluminum has a low work function. In addition, a work function of theorganic photoelectric conversion film 41 on the upper electrode 31 sideis preferably set to a low value. Therefore, by providing a film formedof a material having a low work function such as aluminum on the upperelectrode 31 side of the organic photoelectric conversion unit 41, it ispossible to maintain a low (shallow) work function, to maintainsensitivity, and to improve the sensitivity.

In addition, by providing the metal thin film 102 formed of aluminum orthe like, the metal thin film 102 can prevent entrance of hydrogen orthe like. That is, in this case, the metal thin film 102 can prevent asubstance such as hydrogen from entering the organic photoelectricconversion film 32 from the upper electrode 31 side. Note that the metalthin film 102 is formed so as to have a thickness of 5 nm or less. Withsuch a thickness, the metal thin film 102 can be provided withoutinhibiting light transmittance or causing sensitivity lowering or thelike.

Therefore, it is possible to prevent a substance such as hydrogen fromentering the organic photoelectric conversion film 32 or the lowerelectrode 33 provided on a lower side of the organic photoelectricconversion film 32, and to prevent change of the organic photoelectricconversion film 32 or the lower electrode 33, and reduction of the workfunction.

Note that the work function of the upper electrode 31 is preferablyshallow. Therefore, even when the oxide semiconductor 51 forming theupper electrode 31 is changed due to a substance such as hydrogen, andthe work function becomes shallow, sensitivity of the imaging device 101is not lowered. Therefore, as illustrated in FIG. 3, the metal thin film102 only needs to be provided not on an upper portion (oxidesemiconductor 51) side of the upper electrode 31 but on a lower side(opposite to a light-receiving surface) thereof.

In addition, as illustrated in FIG. 4, the upper electrode 31 may beformed only of the metal thin film 112. In the imaging device 111illustrated in FIG. 4, the upper electrode 31 is formed of the metalthin film 112. When the metal thin film 112 is formed of aluminum or thelike, the metal thin film 112 can function as an electrode. Therefore,the metal thin film 112 may be used as the upper electrode 31.

However, the upper electrode 31 is preferably transparent, and the metalthin film 112 is opaque. Therefore, it is necessary to configure themetal thin film 112 so as to be as thin as possible and to transmitlight.

In addition, in order to prevent the work function of the lowerelectrode 33 from becoming shallow, as illustrated in FIG. 5, the metalthin film 102 may be provided on an upper side of the lower electrode33. In the imaging device 121 illustrated in FIG. 5, the metal thin film122 is provided on the upper side of the lower electrode 33 between thelower electrode 33 and the organic photoelectric conversion film 32.

In the imaging device 121, the metal thin film 122 is provided in theupper portion of the lower electrode 33, and therefore it is possible toprevent a substance such as hydrogen from entering the lower electrode33 and to prevent the lower electrode 33 from being denaturalized.

Incidentally, in a case where the metal thin film 122 is provided on thelower electrode 33 side, when a material of the thin film used as themetal thin film 122 has a deep (high) work function, the work functionof the lower electrode 33 is easily maintained in a deep state, andsensitivity of the imaging device 121 can be maintained.

In addition, similarly to the imaging device 111 illustrated in FIG. 4,the lower electrode 33 itself may be formed of the metal thin film 122.Although not illustrated, the metal thin film 122 may be formed of ametal material having a high work function, and may be caused tofunction as the lower electrode 33.

However, the lower electrode 33 is preferably transparent, and the metalthin film 122 is opaque. Therefore, it is necessary to configure themetal thin film 122 so as to be as thin as possible and to transmitlight.

<Manufacturing of Imaging Device>

Manufacturing of the above imaging device will be described. Here,description will be made by exemplifying a case of manufacturing theimaging device 101 illustrated in FIG. 3. Note that the imaging device111 illustrated in FIG. 4 or the imaging device 121 illustrated in FIG.5 is basically manufactured through similar steps while the order of themanufacturing steps is changed, a step is added, or some of the stepsare omitted.

First, as illustrated in FIG. 6, a so-called SOI substrate 203 in whicha silicon layer 35 is formed on a silicon substrate 202 through asilicon oxide film 201 is prepared. Note that the silicon layer 35corresponds to the above semiconductor substrate 35. The silicon layer35 is formed of an n-type silicon layer.

Subsequently, the first photodiode PD 36 for a second color and thesecond photodiode PD 37 for a third color are formed so as to be stackedon each other at different positions in the depth in the silicon layer35. In this example, the first photodiode PD 36 is formed as aphotodiode absorbing blue wavelength light. The second photodiode PD 37is formed as a photodiode absorbing red wavelength light.

The first photodiode PD 36 is formed by forming a p-type semiconductorregion serving as a hole accumulation layer and an n-type semiconductorregion serving as a charge accumulation layer on a back surface side ofthe silicon layer 35 by ion implantation so as to form a pn junction.

An n-type semiconductor region serving as a charge accumulation layer isformed on a surface side of the silicon layer 35 by ion implantation soas to form a pn junction, and the second photodiode PD 37 is formed ofthe n-type semiconductor region and a p-type semiconductor region in alower layer.

Subsequently, as illustrated in FIG. 8, a multilayer wiring layer 211disposed with a plurality of layers of wiring 212 through an interlayerinsulating film 213 is formed on a surface of the silicon layer 35.

In this example, as the first and second photodiodes PD36 and PD37,photodiodes absorbing red and blue wavelength light have beenexemplified. However, as described above, the combination is notnecessarily limited to the two colors of blue and red.

Subsequently, as illustrated in FIG. 8, a supporting substrate 221 isattached onto the multilayer wiring layer 211. Examples of thesupporting substrate 221 include a silicon substrate.

Subsequently, as illustrated in FIG. 9, the silicon substrate 202 as theinitial SOI substrate 203 and the silicon oxide film 201 are removed,and a back surface of the thin silicon layer 35 is exposed.

Subsequently, as illustrated in FIG. 10, the insulating film 34 isformed on the back surface of the silicon layer 35. This insulating film34 is provided in order to reduce an interface state between theinsulating film 34 and the silicon layer 35 and to suppress generationof a dark current from an interface between the silicon layer 35 and theinsulating film 34. The interface state is preferably small.

As the insulating film 34, for example, a stacked structure film formedof a hafnium oxide (HfO2) film formed by an ALD (atomic layerdeposition) method and a silicon oxide (SiO2) film formed by a plasmaCVD (chemical vapor deposition) method can be used. Note that otherstructures or other film formation methods can be used without beinglimited to the structure and film formation method described here.

Subsequently, as illustrated in FIG. 11, the wiring 39 also serving as alight-shielding film is formed on the silicon layer 35. The wiring 39 isprocessed so as to leave a part to be light-shielded. The wiring 39needs to be in contact with silicon (Si), and is used also as alight-shielding film, and therefore a stacked film formed of a barriermetal Ti and TiN, and tungsten (W) can be used therefor. However, thewiring 39 is not necessarily limited to the structure and the materials.

Subsequently, as illustrated in FIG. 12, the lower electrode 33 servingas a lower electrode of the organic photoelectric conversion unit 41 isformed. For example, the lower electrodes 33 are electrically insulatedfrom each other by an insulating film such as a SiO2 film formed by aplasma CVD method, and flattening is performed by CMP or the like.

It is required for the lower electrode 33 to transmit light. Therefore,for example, a film of ITO is formed by a sputtering method, thenpatterning is performed by a photolithography technique, and processingis performed by dry etching or wet etching.

Note that a material of the lower electrode 33 is not limited to ITO.Examples thereof include tin oxide-based SnO2 (a dopant is added), zincoxide-based materials aluminum zinc oxide (Al is added as a dopant toZnO, for example, AZO), gallium zinc oxide (Ga is added as a dopant toZnO, for example, GZO), and indium zinc oxide (In is added as a dopantto ZnO, for example, IZO), IGZO, CuI, InSbO4, ZnMgO, CuInO2, MgIn2O4,CdO, and ZnSnO3.

Note that the lower electrode 33 is electrically connected to a chargeaccumulation layer 38 through the wiring 39. In addition, either of thewiring 39 and the lower electrode 33 may be patterned first.

Subsequently, as illustrated in FIG. 13, the organic photoelectricconversion film 32 is formed. For example, the organic photoelectricconversion film 32 can be formed of quinacridone by a vacuum vapordeposition method. This example also includes a case where the organicphotoelectric conversion film 32 is formed by stacking an electronblocking and buffer film, a photoelectric conversion film, a holeblocking film, a hole blocking and buffer film, and a work functionadjusting film on the lower electrode 33.

In addition, the organic photoelectric conversion film 32 only needs toinclude at least one of an organic p-type semiconductor and an organicn-type semiconductor, but may have a pin bulk hetero structure includinga p-type blocking layer, a co-vapor deposition layer of a p-type and ann-type, and an n-type blocking layer.

Examples of the organic p-type semiconductor and the organic n-typesemiconductor include a quinacridone derivative, a naphthalenederivative, an anthracene derivative, a phenanthrene derivative, atetracene derivative, a pyrene derivative, a perylene derivative, and afluoranthene derivative.

In addition, a polymer of phenylene vinylene, fluorene, carbazole,indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene orthe like, and a derivative thereof are used. In addition, for example, ametal complex dye, a cyanine dye, a merocyanine dye, a phenylxanthenedye, a triphenylmethane dye, a rhodacyanine dye, a xanthene dye, amacrocyclic azaanulene dye, an azulene dye, naphthoquinone, ananthraquinone dye, a condensed polycyclic aromatic compound such asanthracene or pyrene, a chain compound obtained by condensing anaromatic ring or heterocyclic compound, a heterocyclic ring compoundcontaining two nitrogen atoms and having a squarylium group and acroconic methine group as a bonding chain, such as quinoline,benzothiazole, or benzoxazole, or a cyanine-like dye bonded by asquarylium group and a croconic methine group can be used.

In addition, examples of the metal complex dye include a dithiol metalcomplex dye, a metal phthalocyanine dye, a metal porphyrin dye, and aruthenium complex dye. Note that a dye not illustrated here may be used.

Note that the organic photoelectric conversion film 32 can be formedalso by a coating method.

Subsequently, as illustrated in FIGS. 14 and 15, the upper electrode 31is formed on the organic photoelectric conversion film 32.Characteristics of the organic photoelectric conversion film 32 mayfluctuate due to an influence of moisture, oxygen, hydrogen, or thelike, as described above. Therefore, a film of the upper electrode 31 isformed consistently with the organic photoelectric conversion film 32 invacuum. Here, as described with reference to FIG. 3, the upper electrode31 is formed of the metal thin film 102, the AlO thin film 52, and theoxide semiconductor 51.

For example, the metal thin film 102 can be an Al film made of aluminum(Al), and for example, can be formed by a vacuum vapor depositionmethod. Al has a shallow work function of about 4.3 eV, and is one ofmaterials suitable for a material in contact with the organicphotoelectric conversion film 32.

In addition to Al, examples of a material which can be used as the metalthin film 102 include indium (In), silver (Ag), gold (Au), zinc (Zn),lithium (Li), tin (Sn), antimony (Sb), magnesium (Mg), cadmium (Cd),calcium (Ca), potassium (K), rubidium (Rb), cesium (Cs), strontium (Sr),barium (Ba), cerium (Ce), yttrium (Y), hafnium (Hf), nickel (Ni),gallium (Ga), and titanium (Ti).

Each of these materials may be used singly as the metal thin film 102,these materials may form the metal thin film 102 as a plurality ofcompounds, or a compound formed of a material which has been listed hereand a material which has not been listed here may be used as the metalthin film 102.

Subsequently, the AlO film 52 is formed. For example, when the oxidesemiconductor 51 is formed by a sputtering method after the metal thinfilm 102 is formed of Al, the metal thin film 102 is oxidized by energyof a sputtered particle, and the AlO thin film 52 can be formed easilyso as to have a thickness of about several nm. For example, the AlO thinfilm 52 is formed so as to have a thickness of 20 nm or less.

Here, it has been described that the AlO thin film 52 is formed byoxidizing Al with energy of a sputtered particle. However, the AlO thinfilm 52 may be formed by an ALD method, a CVD method, or the likewithout being limited thereto.

Note that the AlO thin film 52 is an insulating film, but generally hasa sufficiently wide photoelectric conversion area (area of the upperelectrode 31) with respect to the thickness of the AlO film 52, andtherefore can take sufficient electrical conduction by a thermaldiffusion component. It is known that an Al film or an AlO film formedin this manner has a high passivation property with respect to hydrogen.Hydrogen generated during a process can be shielded, and fluctuation ofthe work function of the lower electrode 33 can be suppressed.

In addition, when Al is used as the metal thin film 102, for example,the remaining metal thin film 102 preferably has a thickness of 5 nm orless. This is because sufficient light transmittance can be ensured in athin film region of 5 nm or less although Al has high a light-shieldingproperty.

Subsequently, the oxide semiconductor 51 forming a part of the upperelectrode 31 is formed. The oxide semiconductor 51 is also required tobe transparent with respect to visible light. Here, the description hasbeen made by exemplifying ITO, but the oxide semiconductor 51 is notlimited to ITO. Examples thereof include tin oxide-based SnO2 (a dopantis added), zinc oxide-based materials aluminum zinc oxide (Al is addedas a dopant to ZnO, for example, AZO), gallium zinc oxide (Ga is addedas a dopant to ZnO, for example, GZO), and indium zinc oxide (In isadded as a dopant to ZnO, for example, IZO), IGZO, CuI, InSbO4, ZnMgO,CuInO2, MgIn2O4, CdO, and ZnSnO3.

The upper electrode 31 is formed, and then for example, patterning isperformed by a photolithography technique. Then, the upper electrode 31and the organic photoelectric conversion film 32 are processed by dryetching. Thereafter, post-processing such as ashing or organic cleaningis performed, and a deposit and a residue are removed.

Note that description has been made by exemplifying a case wherepatterning is performed by photolithography and a dry etching method.However, patterning can be performed by using a shadow mask or the like.

Thereafter, the wiring 40 for electrical connection with a passivationfilm (not illustrated) or the upper electrode 31 is formed. Whenpatterning is performed by a dry etching method, a sidewall of theorganic photoelectric conversion film 32 is brought into direct contactwith the passivation film. However, the lower electrode 33 issufficiently separated from the passivation film, and therefore there isalmost no influence. In addition, examples of the wiring 40 includetungsten (W), a barrier metal Ti, TiN, and aluminum (Al), but are notlimited thereto.

For example, the wiring 40 is formed by performing patterning by aphotolithography technique, performing processing by dry etching,performing post-processing such as ashing or organic cleaning, andremoving a deposit and a residue. Thereafter, although not illustrated,a flattened film, an on-chip lens, or the like is formed.

The imaging device 101 is manufactured in this manner. Therefore,hydrogen during a manufacturing process can be shielded so as not toenter the lower electrode 33, and fluctuation of the work function ofthe lower electrode 33 can be suppressed.

Note that this example has exemplified the structure obtained bystacking blue and red photoelectric conversion regions in silicon andstacking a green photoelectric conversion unit on an upper layer of thesilicon. However, the scope of the present technology is not limited tosuch a structure. In addition, description has been made by exemplifyinga back surface irradiation type CMOS imager structure. However, thescope of the present technology is not limited to such a structure.

<Configuration of Second Imaging Device>

Next, a configuration of an imaging device according to a secondembodiment will be described. FIG. 16 is a diagram illustrating theconfiguration of the imaging device according to the second embodiment.In an imaging device 301 illustrated in FIG. 16, similar reference signsare given to similar components to those of the imaging device 101illustrated in FIG. 3, and description thereof will be omitted.

The metal thin film 102 of the imaging device 101 (FIG. 3) according tothe first embodiment is formed into a film shape. However, the imagingdevice 301 according to the second embodiment is different therefrom inthat a film is not formed in the imaging device 301. Here, a metalelectrode 302 is described. As illustrated in FIG. 16, the metalelectrode 302 is provided on a lower side of an AlO film 52 on anorganic photoelectric conversion film 32 side, and is provided in ascattered manner.

In other words, the metal electrode 302 forming the upper electrode 31can have a configuration remaining not in a shape of a film but at anatomic level. Also in the case of this configuration, AlO is present asthe AlO film 52, and therefore a passivation property is ensured.

When the imaging device 301 is viewed from above, as illustrated in FIG.17, the metal electrode 302 is present. The metal electrode 302 may havea spherical shape, a quadrangle shape, or the like, and the shapethereof is not particularly limited. In addition, the metal electrode302 may be disposed at regular intervals, or may be disposed at randomintervals.

In addition, as illustrated in FIG. 18, the metal electrode 302 may beformed into a lattice shape. When the metal electrode 302 is formed intoa lattice shape, the metal electrode 302 may be formed such that a firstphotodiode PD 36 is located in a lattice. In other words, the metalelectrode 302 may be formed so as to be located between the photodiodes.

When the metal electrode 302 is formed into a lattice shape, the metalelectrode 302 can have a light-shielding function. That is, by formingthe metal electrode 302 into a lattice shape, forming the metalelectrode 302 so as to have a width and a thickness capable of obtaininga light-shielding function, and forming the metal electrode 302 at aposition at which the amount of light incident on a photodiode or thelike is not reduced, the metal electrode 302 can be caused to functionas a light-shielding film (light-shielding wall).

Note that when the metal electrode 302 is formed so as to have apredetermined shape such as a lattice shape, the metal electrode 302 canbe formed by applying patterning, a shadow mask, or the like.

<Configuration of Third Imaging Device>

Next, a configuration of an imaging device according to a thirdembodiment will be described. FIG. 19 is a diagram illustrating theconfiguration of the imaging device according to the third embodiment.In an imaging device 401 illustrated in FIG. 19, similar reference signsare given to similar components to those of the imaging device 101illustrated in FIG. 3, and description thereof will be omitted.

The imaging device 401 according to the third embodiment includes a holeblocking layer. In the imaging device 401 illustrated in FIG. 19, a holeblocking layer 402 is provided as a part of an upper electrode 31, andis provided on a lower side of a metal thin film 102 between the metalthin film 102 and an organic photoelectric conversion film 32.

The hole blocking layer 402 is formed of a material such as lithiumfluoride (LiF) or magnesium oxide (MgO). Even when the upper electrode31 including the metal thin film 102 is stacked, a similar effect can beobtained, and a dark current can be reduced.

Note that here, the configuration in which the hole blocking layer 402is provided in the imaging device 101 illustrated in FIG. 3 has beendescribed. However, the hole blocking layer 402 may be provided in theimaging device 111 illustrated in FIG. 4. Although not illustrated, whenthe hole blocking layer 402 is provided in the imaging device 111, thehole blocking layer 402 is provided between the metal thin film 122 andthe organic photoelectric conversion film 32.

In addition, the hole blocking layer 402 may be provided in the imagingdevice 121 illustrated in FIG. 5. Although not illustrated, when thehole blocking layer 402 is provided in the imaging device 121, the holeblocking layer 402 is provided between an AlO film 52 and the organicphotoelectric conversion film 32.

In addition, the hole blocking layer 402 may be provided in the imagingdevice 301 illustrated in FIG. 16. Although not illustrated, when thehole blocking layer 402 is provided in the imaging device 301, the holeblocking layer 402 is provided between the AlO film 52 and the organicphotoelectric conversion film 32. In this case, a metal electrode 302may be provided in the same layer as the hole blocking layer 402, or themetal electrode 302 may be provided between the hole blocking layer 402and the organic photoelectric conversion film 32.

<Configuration of Fourth Imaging Device>

Next, a configuration of an imaging device according to a fourthembodiment will be described. FIG. 20 is a diagram illustrating theconfiguration of the imaging device according to the fourth embodiment.In an imaging device 501 illustrated in FIG. 20, similar reference signsare given to similar components to those of the imaging device 101illustrated in FIG. 3, and description thereof will be omitted.

The imaging device 501 according to the fourth embodiment includes anenthalpy control layer. In the imaging device 501 illustrated in FIG.20, an enthalpy control layer 502 is provided on an upper side of alower electrode 33 between an organic photoelectric conversion film 32and the lower electrode 33.

For example, the enthalpy control layer 502 is formed as an oxide filmcontaining cadmium (Cd), copper (Cu), lead (Pb), palladium (Pd), or thelike. In FIG. 21, materials which can be used as the enthalpy controllayer 502 are listed. As illustrated in FIG. 21, the enthalpy controllayer 502 can be formed of any one of Ag2O, CoO, Co3O4, CdO, Cs2O, CuO,Cu2O, GeO(c), GeO2(c1), GeO2(c2), NiO(c), PbO(c), PbO2(c2), PbO2(c),PdO(c), Rb2O(c), Rb2O2(c), SeO2(c), SeO3(c), TeO2 (C), Tl2O(c), andTl2O3(c).

In FIG. 21, in the column of a transparent electrode, a material whichcan be used for the lower electrode 33 is described. In the column of acomposition, the name of a substance (element symbol) for forming thematerial described in the column of the transparent electrode isdescribed. In the column of a composition of an enthalpy control layer,the name of a substance (element symbol) forming a material which can beused as a material of the enthalpy control layer 502 is described. Inaddition, a numerical value described in association with each elementsymbol is a numerical value of a standard enthalpy of formation.

When the enthalpy control layer 502 is provided, like the imagingdevices according to the first to third embodiments, it is possible toprevent the lower electrode 33 from being denaturalized, and to preventa work function from becoming shallow, for example.

This indicates that in a case where the lower electrode 33 is formed ofITO, for example, when the enthalpy control layer 502 is formed of afilm of copper oxide (CuO), the standard enthalpy of formation (−157.3from FIG. 21) of copper oxide is higher than the standard enthalpy offormation (−280.71 from FIG. 21) of tin oxide (SnO) forming the ITO, andtherefore the enthalpy control layer 502 is reduced selectively.

Therefore, hydrogen does not enter the lower electrode 33, andfluctuation of a work function can be suppressed. Note that the enthalpycontrol layer 502 having a thickness of 5 nm is sufficient.

As described above, by providing the enthalpy control layer 502 in thelower electrode 33, it is possible to prevent a substance such ashydrogen from entering the lower electrode 33, and to prevent a workfunction of the lower electrode 33 from being changed.

Note that the enthalpy control layer 502 may be provided in any one ofthe above imaging devices according to the first to third embodiments.That is, the imaging device can be formed of a combination of any one ofthe metal thin film 102 (FIG. 3), the metal thin film 112 (FIG. 4), themetal thin film 122 (FIG. 5), the metal electrode 302 (FIG. 16), and thehole blocking layer 402 (FIG. 19), and the enthalpy control layer 502.

<Configuration of Electronic Apparatus>

The above imaging device can be applied to any electronic apparatususing a semiconductor device for an image capturing unit (photoelectricconversion unit), such as an imaging device including a digital stillcamera and a video camera, a mobile terminal device having an imagingfunction, including a portable telephone device, or a copying machineusing an imaging device for an image reader.

FIG. 22 is a block diagram exemplifying a structure of an electronicapparatus according to the present technology, for example, an imagingdevice. As illustrated in FIG. 22, an imaging device 1000 according tothe present technology includes an optical system including lenses 1001or the like, an imaging element (imaging device) 1002, a DSP circuit1003, a frame memory 1004, a display device 1005, a recording device1006, an operation system 1007, a power supply system 1008, and thelike. In addition, the DSP circuit 1003, the frame memory 1004, thedisplay device 1005, the recording device 1006, the operation system1007, and the power supply system 1008 are connected to one anotherthrough a bus line 1009.

The lenses 1001 capture incident light (image light) from a subject toform an image on an imaging surface of the imaging element 1002. Theimaging element 1002 converts the amount of the incident light an imageof which has been formed on the imaging surface by the lenses 1001 intoan electrical signal in a pixel unit, and outputs the electrical signalas a pixel signal.

The display device 1005 is formed of a panel display device such as aliquid crystal display device or an organic electro luminescence (EL)display device, and displays a moving image or a still image formed bythe imaging element 1002. The recording device 1006 records the movingimage or the still image formed by the imaging element 1002 in arecording medium such as a digital versatile disk (DVD) or a hard diskdrive (HDD).

The operation system 1007 gives an operation command regarding variousfunctions of the present imaging device under an operation of a user.The power supply system 1008 appropriately supplies various powersources serving as operation power sources for the DSP circuit 1003, theframe memory 1004, the display device 705, the recording device 1006,and the operation system 1007 to these supply targets.

The imaging device having the above configuration can used as an imagingdevice for a video camera, a digital still camera, a cameral module fora mobile apparatus, such as a portable telephone device, or the like. Inaddition, in the imaging device, the above imaging device can be used asthe imaging element 1002.

<Usage Example of Imaging Device>

FIG. 23 is a diagram illustrating a usage example using the aboveimaging device.

As described below, the above imaging device can be used in variouscases of sensing light such as visible light, infrared light,ultraviolet light, or an X-ray.

-   -   a device for taking an image used for appreciation, such as a        digital camera or a portable apparatus with a camera function,    -   a device for transportation use, such as a vehicle-mounted        sensor for imaging the front, the back, the surrounding, the        inside, or the like of an automobile for safe driving such as        automatic stop, for recognition of a driver's condition, and the        like, a surveillance camera for monitoring a running vehicle and        a road, or a measuring sensor for measuring a distance between        vehicles or the like,    -   a device for home electronics use, such as a television set, a        refrigerator, or an air conditioner for imaging a gesture of a        user and operating an apparatus according to the gesture,    -   a device for medical care use and health care use, such as an        endoscope or a device for receiving infrared light for        angiography,    -   a device for security use, such as a surveillance camera for        crime prevention or a camera for personal authentication,    -   a device for beauty care use, such as a skin measurement device        for imaging a skin or a microscope for imaging a scalp,    -   a device for sports use, such as an action camera or a wearable        camera for sports, and    -   a device for agricultural use, such as a camera for monitoring a        condition of a field and a crop.

Note that the effects described here are merely examples, and theeffects of the present technology are not limited thereto, and mayinclude other effects.

Note that embodiments of the present technology are not limited to theabove embodiments, and various modifications can be made to them withoutdeparting from the scope of the present technology.

Note that the present technology can have the following configurations.

(1)

An imaging device including:

an organic photoelectric conversion film;

an upper electrode provided in an upper portion of the organicphotoelectric conversion film;

a lower electrode provided in a lower portion of the organicphotoelectric conversion film; and

a metal thin film provided between the organic photoelectric conversionfilm and the upper electrode or between the organic photoelectricconversion film and the lower electrode.

(2)

The imaging device described in (1), in which

the metal thin film is provided between the organic photoelectricconversion film and the upper electrode, and

the upper electrode is formed of an oxide semiconductor, a metal oxide,and the metal thin film.

(3)

The imaging device described in (2), in which

the metal oxide is aluminum oxide (AlO), and the metal thin film isformed of aluminum (Al).

(4)

The imaging device described in any one of (1) to (3), in which themetal thin film is formed of any one of aluminum (Al), indium (In),silver (Ag), gold (Au), zinc (Zn), lithium (Li), tin (Sn), antimony(Sb), magnesium (Mg), cadmium (Cd), calcium (Ca), potassium (K),rubidium (Rb), cesium (Cs), strontium (Sr), barium (Ba), cerium (Ce),yttrium (Y), hafnium (Hf), nickel (Ni), gallium (Ga), and titanium (Ti).

(5)

The imaging device described in any one of (1) to (4), in which

each of the upper electrode and the lower electrode is formed of any oneof ITO, tin oxide-based SnO2, zinc oxide-based materials aluminum zincoxide, gallium zinc oxide, and indium zinc oxide, IGZO, CuI, InSbO4,ZnMgO, CuInO2, MgIn2O4, CdO, and ZnSnO3.

(6)

The imaging device described in any one of (1) to (5), in which

the organic photoelectric conversion film is formed of any one of aquinacridone derivative, a naphthalene derivative, an anthracenederivative, a phenanthrene derivative, a tetracene derivative, a pyrenederivative, a perylene derivative, and a fluoranthene derivative.

(7)

The imaging device described in any one of (1) to (6), in which theorganic photoelectric conversion film is formed of any one of a polymerof phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole,picoline, thiophene, acetylene, or diacetylene, and a derivativethereof, a metal complex dye, a cyanine dye, a merocyanine dye, aphenylxanthene dye, a triphenylmethane dye, a rhodacyanine dye, axanthene dye, a macrocyclic azaannulene dye, an azulene dye,naphthoquinone, an anthraquinone dye, a condensed polycyclic aromaticcompound such as anthracene or pyrene, a chain compound obtained bycondensing an aromatic ring or heterocyclic compound, a heterocyclicring compound containing two nitrogen atoms and having a squaryliumgroup and a croconic methine group as a bonding chain, such asquinoline, benzothiazole, or benzoxazole, and a cyanine-like dye bondedby a squarylium group and a croconic methine group, and

the metal complex dye is any one of a dithiol metal complex dye, a metalphthalocyanine dye, a metal porphyrin dye, and a ruthenium complex dye.

(8)

The imaging device described in any one of (1) to (7), in which

the metal thin film has a thickness of 5 nm or less.

(9)

The imaging device described in any one of (1) to (8), in which themetal thin film is formed into a spherical shape or a predeterminedshape, and is scattered at equal intervals or at random.

(10)

The imaging device described in any one of (1) to (9), further includinga hole blocking layer between the metal thin film and the organicphotoelectric conversion film.

(11)

The imaging device described in (1), including an enthalpy control layeralong with the metal thin film or in place of the metal thin film.

(12)

The imaging device described in (11), in which the enthalpy controllayer is provided between the organic photoelectric conversion film andthe lower electrode.

(13)

The imaging device described in (11), in which the enthalpy controllayer is formed of any one of Ag2O, CoO, Co3O4, CdO, Cs2O, CuO, Cu2O,GeO(c), GeO2(c1), GeO2(c2), NiO(c), PbO(c), PbO2(c2), PbO2(c), PdO(c),Rb2O(c), Rb2O2(c), SeO2(c), SeO3(c), TeO2 (C), Tl2O(c), and Tl2O3(c).

(14)

A manufacturing device for

forming an organic photoelectric conversion film,

forming an upper electrode in an upper portion of the organicphotoelectric conversion film,

forming a lower electrode in a lower portion of the organicphotoelectric conversion film, and

forming a metal thin film between the organic photoelectric conversionfilm and the upper electrode or between the organic photoelectricconversion film and the lower electrode.

(15)

The manufacturing device described in (14), in which the metal thin filmis formed by vapor deposition.

(16)

The manufacturing device described in (14) or (15), in which

the metal thin film is formed between the organic photoelectricconversion film and the upper electrode,

the upper electrode is formed by stacking an oxide semiconductor, ametal oxide, and the metal thin film, and

the metal oxide is formed by oxidization at the time of film formationof the oxide semiconductor.

(17)

The manufacturing device described in any one of (14) to (16), in whichthe metal thin film is formed into a spherical shape or a predeterminedshape so as to be scattered at equal intervals or at random.

(18)

The manufacturing device described in any one of (14) to (16), in which

a hole blocking layer is further formed between the metal thin film andthe organic photoelectric conversion film.

(19)

The manufacturing device described in any one of (14) to (16), in which

an enthalpy control layer is formed along with the metal thin film or inplace of the metal thin film.

(20)

A manufacturing device for

forming an organic photoelectric conversion film,

a step of forming an upper electrode in an upper portion of the organicphotoelectric conversion film;

a step of forming a lower electrode in a lower portion of the organicphotoelectric conversion film; and

a step of forming a metal thin film between the organic photoelectricconversion film and the upper electrode or between the organicphotoelectric conversion film and the lower electrode.

REFERENCE SIGNS LIST

-   31 upper electrode-   32 organic photoelectric conversion film-   33 lower electrode-   34 insulating film-   35 substrate-   36 first photodiode PD-   37 second photodiode PD-   102, 112, 122 metal thin film-   302 metal electrode-   402 hole blocking layer-   502 enthalpy control layer

1. An imaging device, comprising: an organic photoelectric conversionfilm; an upper electrode in an upper portion of the organicphotoelectric conversion film; a lower electrode in a lower portion ofthe organic photoelectric conversion film; and an enthalpy control layerbetween the organic photoelectric conversion film and the lowerelectrode.
 2. (canceled)
 3. The imaging device according to claim 1,wherein the enthalpy control layer includes an oxide film containing oneof cadmium (Cd), copper (Cu), lead (Pb), or palladium (Pd).
 4. Theimaging device according to claim 1, wherein the enthalpy control layerincludes one of a Silver Oxide (Ag₂O), Cobalt(II) Oxide (CoO), Cobalt(II, III) Oxide (Co₃O₄), Cesium oxide (Cs₂O), Copper Oxide (CuO),Cuprous Oxide (Cu₂O), Germanium oxide (GeO), Germanium dioxide (GeO₂),Nickel Oxide (NiO), or Lead Oxide (PbO).
 5. The imaging device accordingto claim 1, wherein the enthalpy control layer has a thickness of one ofequal to 5 nm or less than 5 nm.
 6. The imaging device according toclaim 1, further comprising a metal thin film between the organicphotoelectric conversion film and the upper electrode.
 7. The imagingdevice according to claim 6, wherein the upper electrode comprises ahole blocking layer, and the hole blocking layer is between the metalthin film and the organic photoelectric conversion film.
 8. The imagingdevice according to claim 6, wherein the metal thin film includesaluminum (Al).
 9. The imaging device according to claim 6, wherein themetal thin film includes one of aluminum (Al), indium (In), silver (Ag),gold (Au), zinc (Zn), lithium (Li), tin (Sn), antimony (Sb), magnesium(Mg), cadmium (Cd), calcium (Ca), potassium (K), rubidium (Rb), cesium(Cs), strontium (Sr), barium (Ba), cerium (Ce), yttrium (Y), hafnium(Hf), nickel (Ni), gallium (Ga), or titanium (Ti).
 10. The imagingdevice according to claim 1, wherein the lower electrode comprises anmetal oxide layer, and the metal oxide layer is disposed between theorganic photoelectric conversion film and the lower electrode.
 11. Theimaging device according to claim 1, wherein each of the upper electrodeand the lower electrode includes one of ITO, tin oxide-based SnO2,aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, IGZO, CuI,InSbO4, ZnMgO, CuInO2, MgIn2O4, CdO, or ZnSnO3.
 12. The imaging deviceaccording to claim 1, wherein the organic photoelectric conversion filmincludes one of a quinacridone derivative, a naphthalene derivative, ananthracene derivative, a phenanthrene derivative, a tetracenederivative, a pyrene derivative, a perylene derivative, or afluoranthene derivative.
 13. The imaging device according to claim 1,wherein the organic photoelectric conversion film includes one of apolymer, a metal complex dye, a cyanine dye, a merocyanine dye, aphenylxanthene dye, a triphenylmethane dye, a rhodacyanine dye, axanthene dye, a macrocyclic azaannulene dye, an azulene dye,naphthoquinone, an anthraquinone dye, a condensed polycyclic aromaticcompound, a chain compound, a heterocyclic ring compound, or a firstdye.
 14. The imaging device according to claim 13, wherein the polymeris one of phenylene vinylene, fluorene, carbazole, indole, pyrene,pyrrole, picoline, thiophene, acetylene, or diacetylene, the metalcomplex dye is one of a dithiol metal complex dye, a metalphthalocyanine dye, a metal porphyrin dye, or a ruthenium complex dye,the condensed polycyclic aromatic compound is one of anthracene orpyrene, the chain compound is one of a condensed aromatic ring or acondensed heterocyclic compound, the heterocyclic ring compound is oneof quinoline, benzothiazole, or benzoxazole, and the first dye is bondedby one of a squarylium group or a croconic methine group.
 15. Theimaging device according to claim 1, wherein the upper electrodecomprises an oxide semiconductor, a metal oxide, and a metal thin film,the oxide semiconductor, the metal oxide, and the metal thin film arestacked, and the metal oxide is an oxidized portion of the metal thinfilm.
 16. The imaging device according to claim 1, wherein a standardenthalpy of formation of a material of the enthalpy control layer ishigher than a standard enthalpy of formation of a material of the lowerelectrode, and the enthalpy control layer is reduced selectively. 17.The imaging device according to claim 16, wherein the enthalpy controllayer is configured to prevent hydrogen from entering the lowerelectrode.
 18. The imaging device according to claim 1, wherein theupper electrode comprises an oxide semiconductor (ITO) and an aluminumoxide (AlO) thin film.